CN110628436A - Compound eluting agent for repairing heavy metal contaminated soil and application thereof - Google Patents
Compound eluting agent for repairing heavy metal contaminated soil and application thereof Download PDFInfo
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- CN110628436A CN110628436A CN201910754763.8A CN201910754763A CN110628436A CN 110628436 A CN110628436 A CN 110628436A CN 201910754763 A CN201910754763 A CN 201910754763A CN 110628436 A CN110628436 A CN 110628436A
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- soil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
Abstract
The invention belongs to the field of contaminated soil remediation, and discloses a compound eluent for remediating heavy metal contaminated soil and application thereof. The compound eluting agent is prepared by compounding a sodium humate solution with the concentration of 0.0125-0.2 mol/L and a citric acid solution with the concentration of 0.0125-0.1 mol/L according to the volume ratio of 1: 3-3: 1. The application of the compound eluent in treating Cu and Zn polluted soil is characterized in that: the application comprises the following steps: weighing a pre-treated soil sample, adding a compound eluent according to a solid-to-liquid ratio (g: ml) of 1: 10-1: 40, and preliminarily mixing uniformly; placing the preliminarily mixed and uniform sample in an oscillator for carrying out uniform oscillation reaction for 4-8 h to ensure that the soil is fully contacted with the eluting agent; and taking out the sample after oscillation, carrying out centrifugal solid-liquid separation, and determining the concentration of the heavy metal in the supernatant.
Description
Technical Field
The invention belongs to the field of contaminated soil remediation, and particularly relates to a compound eluent for remediating heavy metal contaminated soil and application thereof.
Background
At present, the urbanization process of China is continuously accelerated, urban development land faces a severe test, and how to better utilize urban land becomes a problem which must be considered by local governments. In the process of land recycling, soil pollution becomes an important problem to be solved. Due to the restriction of early production technology level and irregular pollutant discharge, the pollution condition of large-scale industrial sites is serious, and the problem of treatment and reutilization of brown lands seriously restricts the development of cities.
As a soil remediation technology with high speed, high efficiency and convenient operation, a soil leaching treatment technology is concerned. The action mechanism of the soil leaching is that the leaching agent or the chemical auxiliary agent is combined with the pollutants in the soil, and the purpose of repairing the polluted soil is achieved through the chemical actions of desorption, chelation, dissolution or fixation and the like of the leaching agent. At present, the eluting agents can be mainly divided into inorganic eluting agents, artificial chelating agents and biological surfactants, although the eluting agents have a certain removing effect on soil heavy metals, the inorganic eluting agents easily cause the over-strong acidity of the soil after elution, the artificial chelating agents easily cause secondary pollution, and the biological surfactants are expensive, so that the selection of one of the environment-friendly and low-price eluting agents has important significance for repairing the soil polluted by the heavy metals.
The invention discloses a compound heavy metal heavily-polluted soil eluting agent and a method thereof, and application number 201710364113.3 discloses a method for restoring heavily-polluted As, Cd, Cr, Ni, Pb and Zn soil by compounding ferric chloride and citric acid. The invention discloses a compound eluent for repairing heavy metal compound contaminated soil and a using method thereof in China, and application number 201710519506.7 discloses a method for repairing soil and treating eluent by using an EDTA and citric acid compound eluent. In addition, NaOH solution is needed to adjust the pH value of the eluent in the application process, and the operation is complicated.
In a word, although the existing eluting agent has certain removal efficiency on heavy metals in soil, the existing eluting agent has great influence on the physicochemical property of the soil, new pollutants can be brought after the eluting, the treatment cost is high, and how to overcome the problems becomes a problem which needs to be solved urgently in the field.
Disclosure of Invention
In order to overcome the defects of the eluent, the invention provides a preparation method of a compound eluent for repairing heavy metal contaminated soil.
The invention also aims to provide application of the compound eluting agent for repairing heavy metal contaminated soil.
The purpose of the invention is realized by the following technical scheme:
the compound eluting agent for repairing heavy metal contaminated soil is prepared by compounding 0.0125-0.2 mol/L sodium humate solution and 0.0125-0.1 mol/L citric acid solution according to a volume ratio of 1: 3-3: 1.
Preferably, the volume ratio of the sodium humate solution to the citric acid solution is 1:3, 1:2, 1:1, 2:1 or 3: 1.
The preparation method of the compound eluting agent is characterized in that a sodium humate solution with the concentration of 0.0125-0.2 mol/L and a citric acid solution with the concentration of 0.0125-0.1 mol/L are mixed according to the volume ratio of 1: 3-3: 1 to obtain the compound eluting agent.
The application of the compound eluent for repairing heavy metal contaminated soil in the treatment of Cu and Zn contaminated soil comprises the following steps:
(1) weighing a pre-treated soil sample, adding a compound eluent, and preliminarily mixing uniformly;
(2) placing the preliminarily mixed and uniform sample in a water bath constant temperature oscillator for uniform oscillation reaction to ensure that the soil is fully contacted with the eluting agent;
(3) and taking out the sample after oscillation, carrying out centrifugal solid-liquid separation, and determining the concentration of the heavy metal in the supernatant.
And (2) the pretreatment in the step (1) is to air-dry a soil sample, grind, screen out large soil blocks and impurities, and screen through a 40-80-mesh sieve.
The dosage of the compound eluting agent in the step (1) is calculated according to the use amount of 10-40 ml of the compound eluting agent per gram of soil sample.
The oscillating speed in the step (2) is 150-190 r/min, and the reaction time is 4-8 h.
The rotation speed of the centrifugation in the step (3) is 3400r/min, and the centrifugation time is 15 min.
The heavy metal removal rate Cu in the step (3) is 61.8-78.9%, and the Zn is 35.4-53.8%.
The invention compounds low-concentration citric acid and sodium humate with soil improvement effect to be used as a composite eluting agent. On one hand, the sodium humate contains more active groups such as hydroxyl, quinonyl, carboxyl and the like, has a large internal surface area, and has strong adsorption, ion exchange and complexing capabilities; on the other hand, the citric acid has functional groups such as-COOH, -OH and the like, has good heavy metal complexing capacity and certain acidity, is beneficial to the analysis of heavy metals from the surface of soil particles, and further enhances the removal efficiency of the heavy metals.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the low-concentration citric acid and the sodium humate are compounded, and the acid dissolution promotes the analysis of heavy metal ions, so that the complexing of heavy metals by the components of the compound eluent is facilitated, and the removal efficiency of heavy metals Cu and Zn in soil is improved.
(2) According to the invention, the low-concentration citric acid and the sodium humate are compounded, so that the problems of soil acidification, soil nutrient loss and the like caused by over-strong acidity of the citric acid can be solved, the compound eluent is weakly acidic or neutral, the influence on the physical and chemical properties of the soil is small, in addition, the sodium humate has a certain improvement effect on the soil, and the content of organic matters and other nutrient elements in the soil can be increased.
(3) The method is simple to operate, the pH value of the soil does not need to be adjusted in the operation process, the concentration of the required reagent is low, the price is low, and the treatment cost is greatly reduced.
(4) The main components of the compound eluting agent used in the invention are low-concentration sodium humate and citric acid solution, both of which have good biodegradability and can not cause secondary pollution.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The soil used in the following examples is actual contaminated site soil, and the relevant properties are shown in table 1 below:
TABLE 1 physicochemical Properties of the soil tested
Example 1
(1) Naturally air-drying the actual soil with the Cu content of 12843.16mg/kg and the Zn content of 9725.10mg/kg, grinding, and sieving with a 60-mesh sieve;
(2) respectively mixing 0.03mol/L sodium humate solution and 0.03mol/L citric acid solution in a volume ratio of 1:3 to obtain a compound eluting agent;
(3) weighing 2.0g of soil sample in a 50ml centrifuge tube, and adding 80ml of compound eluent according to the solid-to-liquid ratio (g: ml) of 1: 40;
(4) placing the centrifugal tube in an oscillator at 25 ℃, shaking at a constant speed of 185r/min for 6h, centrifuging at 3400r for 15min, taking supernate, filtering with a 0.45 mu m filter membrane, and measuring the concentrations of Cu and Zn in the supernate;
experimental results show that the leaching efficiency of the compound leaching agent to Cu and Zn heavy metals under the condition is 64.0% and 51.9% respectively.
Example 2
(1) Naturally air-drying the actual soil with the Cu content of 12843.16mg/kg and the Zn content of 9725.10mg/kg, grinding, and sieving with a 60-mesh sieve;
(2) respectively mixing 0.03mol/L sodium humate solution and 0.03mol/L citric acid solution in a volume ratio of 1:2 to obtain a compound eluting agent;
(3) weighing 2.0g of soil sample in a 50ml centrifuge tube, and adding 80ml of compound eluent according to the solid-to-liquid ratio (g: ml) of 1: 40;
(4) placing the centrifugal tube in an oscillator at 25 ℃, shaking at a constant speed of 185r/min for 6h, centrifuging at 3400r for 15min, taking supernate, filtering with a 0.45 mu m filter membrane, and measuring the concentrations of Cu and Zn in the supernate;
experimental results show that the leaching efficiency of the compound leaching agent to Cu and Zn heavy metals under the condition is 64.7% and 53.8% respectively.
Example 3
(1) Naturally air-drying the actual soil with the Cu content of 12843.16mg/kg and the Zn content of 9725.10mg/kg, grinding, and sieving with a 60-mesh sieve;
(2) respectively mixing 0.03mol/L sodium humate solution and 0.03mol/L citric acid solution in a volume ratio of 1:1 to obtain a compound eluting agent;
(3) weighing 2.0g of soil sample into a 50ml centrifuge tube, and adding 40ml of compound eluent according to the solid-to-liquid ratio (g: ml) of 1: 20;
(4) placing the centrifugal tube in an oscillator at 25 ℃, shaking at a constant speed of 185r/min for 6h, centrifuging at 3400r for 15min, taking supernate, filtering with a 0.45 mu m filter membrane, and measuring the concentrations of Cu and Zn in the supernate;
by calculation, the removal efficiency of the compound eluent on Cu and Zn can reach 65.6 percent and 43.7 percent respectively under the condition.
Example 4
(1) Naturally air-drying the actual soil with the Cu content of 12843.16mg/kg and the Zn content of 9725.10mg/kg, grinding, and sieving with a 60-mesh sieve;
(2) respectively mixing 0.2mol/L sodium humate solution and 0.05mol/L citric acid solution in a volume ratio of 2:1 to obtain a compound eluting agent;
(3) weighing 2.0g of soil sample into a 50ml centrifuge tube, and adding 40ml of compound eluent according to the solid-to-liquid ratio (g: ml) of 1: 20;
(4) placing the centrifugal tube in an oscillator at 25 ℃, shaking at a constant speed of 185r/min for 6h, centrifuging at 3400r for 15min, taking supernate, filtering with a 0.45 mu m filter membrane, and determining the content of Cu and Zn;
experimental results show that the leaching efficiency of the compound leaching agent to Cu and Zn heavy metals under the condition is 78.9% and 36.5% respectively.
Example 5
(1) Naturally air-drying the actual soil with the Cu content of 12843.16mg/kg and the Zn content of 9725.10mg/kg, grinding, and sieving with a 60-mesh sieve;
(2) respectively mixing 0.1mol/L sodium humate solution and 0.03mol/L citric acid solution according to the volume ratio of 3:1 to obtain a compound eluting agent;
(3) weighing 2.0g of soil sample into a 100ml centrifuge tube, and adding 40ml of compound eluent according to the solid-to-liquid ratio (g: ml) of 1: 20;
(4) placing the centrifugal tube in an oscillator at 25 ℃, shaking at a constant speed of 185r/min for 6h, centrifuging at 3400r for 15min, taking supernate, filtering with a 0.45 mu m filter membrane, and measuring the concentrations of Cu and Zn in the supernate;
experimental results show that the leaching efficiency of the compound leaching agent to Cu and Zn heavy metals under the condition is 61.8% and 35.4% respectively.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A compound eluent for repairing heavy metal contaminated soil is characterized in that: the compound eluting agent is prepared by compounding a sodium humate solution with the concentration of 0.0125-0.2 mol/L and a citric acid solution with the concentration of 0.0125-0.1 mol/L according to the volume ratio of 1: 3-3: 1.
2. The compound eluent for remediating heavy metal contaminated soil as recited in claim 1, wherein: the volume ratio of the sodium humate solution to the citric acid solution is 1:3, 1:2, 1:1, 2:1 or 3: 1.
3. The application of the compound eluent for remediating heavy metal contaminated soil as recited in claim 1 in the treatment of Cu and Zn contaminated soil is characterized in that: the application comprises the following steps:
(1) weighing a pre-treated soil sample, adding a compound eluent, and preliminarily mixing uniformly;
(2) placing the preliminarily mixed and uniform sample in a water bath constant temperature oscillator for uniform oscillation reaction to ensure that the soil is fully contacted with the eluting agent;
(3) and taking out the sample after oscillation, carrying out centrifugal solid-liquid separation, and determining the concentration of the heavy metal in the supernatant.
4. Use according to claim 3, characterized in that: and (2) the pretreatment in the step (1) is to air-dry a soil sample, grind, screen out large soil blocks and impurities, and screen through a 40-80-mesh sieve.
5. Use according to claim 3, characterized in that: the dosage of the compound eluting agent in the step (1) is calculated according to the use amount of 10-40 ml of the compound eluting agent per gram of soil sample.
6. Use according to claim 3, characterized in that: the oscillating speed in the step (2) is 150-190 r/min, and the reaction time is 4-8 h.
7. Use according to claim 3, characterized in that: the rotation speed of the centrifugation in the step (3) is 3400r/min, and the centrifugation time is 15 min.
8. Use according to claim 3, characterized in that: the heavy metal removal rate Cu in the step (3) is 61.8-78.9%, and the Zn is 35.4-53.8%.
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Application publication date: 20191231 |